DOCSLIB.ORG

Carboxylic Acid Derivatives and Nucleophilic Acyl Substitution Reactions

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Carboxylic Acid Derivatives and Nucleophilic Acyl Substitution Reactions Carboxylic Acid Derivatives and Nucleophilic Acyl Substitution Reactions McMurrayMcMurray TextText ChapterChapter 2121 Carboxylic Acid Derivatives O O R OH R X Acid Halide O O O O R OR' R NH2 Amide (1°) Ester R O R' Acid Anhydride NomenclatureNomenclature Acid Halides (Acyl Halides) ChangeChange “–“–icic acidacid”” inin thethe parentparent carboxyliccarboxylic acidacid toto “–yl” followedfollowed byby thethe halide. O O Cl H3C Cl Cl acetyl chloride O (from acetic acid) O hexanedioyl chloride (from hexanedioic acid) H3CH2CHC Cl 2-methylbutanoyl chloride CH3 (from 2-methylbutanoic acid) NomenclatureNomenclature Symmetrical Acid Anhydrides ChangeChange ““acidacid”” inin thethe parentparent carboxyliccarboxylic acidacid toto “anhydride.” O O O O O O acetic anhydride butanoic anhydride (from 2 acetic acids) (from 2 butanoic acids) NomenclatureNomenclature Unsymmetrical Acid Anhydrides NameName thethe twotwo acidsacids alphabeticallyalphabetically andand changechange ““acidacid”” toto “anhydride.” O O O O O O H acetic benzoic anhydride ethanoic methanoic anhydride NomenclatureNomenclature Esters Name R group bondedbonded toto O,O, followedfollowed byby replacingreplacing “–“–icic acidacid”” inin thethe parentparent acidacid withwith “–ate.” O O O O EtO OEt ethyl acetate diethyl propanedioate O O O O methyl butanoate isopentyl acetate NomenclatureNomenclature Amides 1° amides: ChangeChange “–“–oicoic acidacid”” (IUPAC)(IUPAC) oror ““--icic acidacid”” (common)(common) inin thethe parentparent acidacid toto “–amide.” O acetamide NH2 2° and 3° amides: FirstFirst identifyidentify thethe substituentsubstituent groupsgroups (preceded(preceded byby ““NN--””)and)and thenthen thethe parentparent amide.amide. O O H N H N N-Methylacetamide N,N-Dimethylformamide NucleophilicNucleophilic AcylAcyl SubstitutionSubstitution O O O + Nu + Lv R R Lv Nu Lv R Nu tetrahedral intermediate ReactivityReactivity ofof AcidAcid Derivatives:Derivatives: StericSteric EffectsEffects O O O O R H H H C < C < C C R < R H H R R R H Reactivity toward nucleophilic substitution Most Hindered Least Hindered ReactivityReactivity ofof AcidAcid Derivatives:Derivatives: ElectronicElectronic EffectsEffects O O O O O < < < R NH2 R OR' R O R' R X Amide Ester Acid Anhydride Acid Halide Reactivity toward nucleophilic substitution Carbonyl carbon Carbonyl carbon least electrophilic most electrophilic NucleophilicNucleophilic AcylAcyl SubstitutionSubstitution RxnsRxns O Alcoholysis O Reduction H- 1 R H R OR R1OH H- Grignard O O Reagent R1MgX 1 R R1 R Y R MgX O O Aminolysis Hydrolysis R OH R NH H O 2 NH3 2 PreparationPreparation ofof AcylAcyl HalidesHalides O SOCl2 O R Cl PBr R OH 3 O R Br Note: Acid fluorides are extremely reactive and require different preparation methods. PreparationPreparation ofof AnhydridesAnhydrides O O O Heat 2 R OH R O R + H2O Carboxylic Carboxylic acid acid Anhydride O COOH Heat O + H O Cyclic Anhydride COOH 2 O Succinic acid Succinic anhydride O O O O O R1 Cl NaOH Mixed Anhydride R OH R O-Na+ R O R1 PreparationPreparation ofof EstersEsters Fischer Esterification O O H+ R OH R OR1 + H2O R1OH + H H H O H O OH O R1 R1 R OH R OH R O R O HO H HO R1OH H H O O O -H O H Note: If one uses labeled alcohol, the 2 label is retained in the product. R OR1 R OR1 PreparationPreparation ofof AmidesAmides NoNo simplesimple methodmethod forfor thethe preparationpreparation ofof amidesamides fromfrom carboxyliccarboxylic acids!acids! AmidesAmides fromfrom acidsacids discusseddiscussed inin 26.1026.10 InterconversionInterconversion ofof DerivativesDerivatives AllAll acidacid derivativesderivatives cancan bebe convertedconverted toto carboxyliccarboxylic acids.acids. AA derivativederivative can bebe convertedconverted toto aa lessless reactivereactive derivative.derivative. AA derivativederivative cannot bebe convertedconverted toto aa moremore reactivereactive derivative.derivative. AnhydridesAnhydrides cancan bebe convertedconverted toto estersesters andand amides,amides, butbut notnot intointo acidacid halides.halides. InterconversionInterconversion LectureLecture 22 (with(with review)review) ReactivityReactivity ofof AcidAcid Derivatives:Derivatives: ElectronicElectronic EffectsEffects O O O O O < < < R NH2 R OR' R O R' R X Amide Ester Acid Anhydride Acid Halide Reactivity toward nucleophilic substitution Carbonyl carbon Carbonyl carbon least electrophilic most electrophilic NomenclatureNomenclature AcidAcid chloride:chloride: ““--ylyl chloridechloride”” Anhydride:Anhydride: ““anhydrideanhydride”” Ester:Ester: ““-ate-ate”” O Amide:Amide: ““amideamide”” O O isopentyl acetate H3C Cl acetyl chloride (from acetic acid) NucleophilicNucleophilic AcylAcyl SubstitutionSubstitution O O O + Nu + Lv R R Lv Nu Lv R Nu tetrahedral intermediate InterconversionInterconversion AcidAcid HalideHalide HydrolysisHydrolysis O O OH2 OH2 R Cl R Cl OH O O Acid H R OH R O H A base such as pyridine, triethylamine, or NaOH is used to remove the HCl that is formed. AcidAcid HalidesHalides intointo AnhydridesAnhydrides Acid chloride/carboxylate reaction useful for preparing either symmetrical or unsymmetrical anhydrides. O O O O O OH NaOH O-Na+ H3C Cl O CH3 Mixed Anhydride AcidAcid HalideHalide AlcoholysisAlcoholysis O OH N + + Cl O NH Cl + O Ester AcidAcid HalideHalide AminolysisAminolysis O O C 2 NH3 C Cl NH2 + NH4Cl Formation of a primary amide Benzoyl Chloride Benzamide O H O 2 H N C C H Cl CH3 N + CH3NH3Cl Formation of a secondary amide CH3 O 2 H N O C H - CH N + N Cl Formation of a tertiary amide C 3 H CH Cl CH3 3 NH O Cl Cl O N H m-toluyl chloride O N O N 3° amide! H Cl N,N-diethyl-m-toluamide (DEET) AcidAcid HalideHalide ReductionReduction O O H H 1. LAH LAH C 1 C C R OClR + R H R OH 2. H3O Ester Aldehyde Primary alcohol O O 1 R1 R R1MgX R1MgX C C 1 C R Cl R R R OH Grignard Reagent Ketone Tertiary alcohol AcidAcid HalidesHalides intointo KetonesKetones Gilman reagent: R2CuLi (lithium diorganocopper) O O C (CH ) CuLi C Cl 3 2 CH3 No overoxidation as opposed to Grignard reactions! Note: Carboxylic acids, esters, acid anhydrides, and amides do not react with Gilman reagents. AcidAcid AnhydrideAnhydride ReactionsReactions Less reactive than acid chlorides, but react in a similar fashion… HydrolysisHydrolysis React with water to form carboxylic acids AlcoholysisAlcoholysis React with alcohols to form esters AminolysisAminolysis React with amines to form amides ReductionReduction React with LiAlH4 to form 1° alcohols AcidAcid AnhydrideAnhydride Alcoholysis: Ester Aminolysis: Amide EsterEster HydrolysisHydrolysis base-catalyzed hydrolysis (saponification) O CH2O C (CH2)16CH3 CH2OH O O NaOH CHO C (CH2)16CH3 CHOH + 3 H3C(CH2)16 C ONa H2O O CH2O C (CH2)16CH3 CH2OH Triglyceride Glycerol Sodium Stearate Soap O O O O C C - 1 R OR1 R OR1 C + R1O C + R OH R OH R O OH OH EsterEster HydrolysisHydrolysis acid-catalyzed hydrolysis (reverse Fischer Esterification) H H H H O O O O O C 1 C 1 C C R1 C 1 R OR R OR R OR1 R O R OH + R OH O O H H H H O H H H H O O O H + C C + H3O R OH R OH Acid EsterEster AminolysisAminolysis Esters react with ammonia and with 1° and 2° amines to form amides. O Ph + NH3 OEt O Ph + EtOH NH2 EsterEster ReductionReduction O O H H 1. LAH LAH C 1 C C R OR + R H R OH 2. H3O Ester Aldehyde Primary alcohol O O 1 R1 R R1MgX R1MgX C C 1 C R ORCl R R R OH Grignard Reagent Ketone Tertiary alcohol AmideAmide HydrolysisHydrolysis O O Acid 1. HO C C R NH2 + R OH 2. H3O AmideAmide ReductionReduction AmidesAmides intointo AminesAmines usingusing LiAlHLiAlH4 ProductProduct ofof reductionreduction isis anan amine,amine, notnot anan alcoholalcohol asas withwith thethe otherother acidacid derivativesderivatives O 1. LAH H H C C R NH2 + R NH2 2. H3O Primary amine H H OAlH3 N O H H C C C C R NH2 R NH2 R H R NH2 H H H Primary amine NucleophilicNucleophilic SubstitutionSubstitution RxnsRxns SummarySummary Product Starting Acid Acid Carboxylic Ester Amide Material Chloride Anhydride Acid Acid Chloride - Rxn Rxn Rxn Rxn Acid Anhydride 0 - Rxn Rxn Rxn Carboxylic Acid Rxn Rxn - Rxn Rxn Ester 0 0 Rxn - Rxn Amide 0 0 Rxn 0 - 0 = No reaction.
Load more

Recommended publications
  • Amide Bond Formation and Peptide Coupling
    Tetrahedron 61 (2005) 10827–10852 Tetrahedron report number 740 Amide bond formation and peptide coupling Christian A. G. N. Montalbetti* and Virginie Falque Evotec, 112 Milton Park, Abingdon OX14 4SD, UK Received 2 August 2005 Available online 19 September 2005 Contents 1. Introduction ................................................................. 10828 2. Amide bond formation: methods and strategies ....................................... 10828 2.1. Acyl halides . .......................................................... 10829 2.1.1. Acyl chlorides .................................................... 10829 2.1.1.1. Acyl chloride formation ...................................... 10829 2.1.1.2. Coupling reactions with acyl chlorides ........................... 10831 2.1.1.3. Limitations of acyl chlorides .................................. 10831 2.1.2. Acyl fluorides .................................................... 10831 2.1.3. Acyl bromides .................................................... 10832 2.2. Acyl azides . .......................................................... 10832 2.3. Acylimidazoles using CDI ................................................. 10833 2.4. Anhydrides . .......................................................... 10834 2.4.1. Symmetric anhydrides .............................................. 10834 2.4.2. Mixed anhydrides .................................................. 10834 2.4.2.1. Mixed carboxylic anhydrides .................................. 10834 2.4.2.2. Mixed carbonic anhydrides ...................................
    [Show full text]
  • The Radiochemistry of Beryllium
    National Academy of Sciences National Research Council I NUCLEAR SCIENCE SERIES The Radiochemistry ·of Beryllium COMMITTEE ON NUCLEAR SCIENCE L. F. CURTISS, Chairman ROBLEY D. EVANS, Vice Chairman National Bureau of Standards MassaChusetts Institute of Technol0gy J. A. DeJUREN, Secretary ./Westinghouse Electric Corporation H.J. CURTIS G. G. MANOV Brookhaven National' LaboratOry Tracerlab, Inc. SAMUEL EPSTEIN W. WAYNE MEINKE CalUornia Institute of Technology University of Michigan HERBERT GOLDSTEIN A.H. SNELL Nuclear Development Corporation of , oak Ridge National Laboratory America E. A. UEHLING H.J. GOMBERG University of Washington University of Michigan D. M. VAN PATTER E.D.KLEMA Bartol Research Foundation Northwestern University ROBERT L. PLATZMAN Argonne National Laboratory LIAISON MEMBERS PAUL C .. AEBERSOLD W.D.URRY Atomic Energy Commission U. S. Air Force J. HOW ARD McMILLEN WILLIAM E. WRIGHT National Science Foundation Office of Naval Research SUBCOMMITTEE ON RADIOCHEMISTRY W. WAYNE MEINKE, Chairman HAROLD KIRBY University of Michigan Mound Laboratory GREGORY R. CHOPPIN GEORGE LEDDICOTTE Florida State University. Oak Ridge National Laboratory GEORGE A. COW AN JULIAN NIELSEN Los Alamos Scientific Laboratory Hanford Laboratories ARTHUR W. FAIRHALL ELLIS P. STEINBERG University of Washington Argonne National Laboratory JEROME HUDIS PETER C. STEVENSON Brookhaven National Laboratory University of California (Livermore) EARL HYDE LEO YAFFE University of CalUornia (Berkeley) McGill University CONSULTANTS NATHAN BALLOU WILLIAM MARLOW Naval Radiological Defense Laboratory N atlonal Bureau of Standards JAMESDeVOE University of Michigan CHF.MISTRY-RADIATION AND RADK>CHEMIST The Radiochemistry of Beryllium By A. W. FAIRHALL. Department of Chemistry University of Washington Seattle, Washington May 1960 ' Subcommittee on Radiochemistry National Academy of Sciences - National Research Council Printed in USA.
    [Show full text]
  • B.Sc.(H) Chemistry-3Rd Semester
    LIBRARY (18 [This question paper contains 4 printed pages Your Roll No. S1. No. of Q. Paper :7393 J Unique Paper Code 32171301 Name of the Course : B.Sc.(Hons.) Chemistry Name of the Paper Inorganic Chemistry II: s and p block elements Semester : II Time: 3 Hours Maximum Marks : 75 Instructions for Candidates: (i) Write your Roll No.. on the top immediately on receipt of this question paper. (ii) Attempt any five questions. (iii) All questions carry equal marks. 1. (a) Explain why most lines in the Ellingham diagram slope upward from left to right. What happens when a line crosses AG=0? 5 (b) Why is white phosphorus very reactive in comparison to red phosphorus ? Give the mechanism of stepwise hydrolysis of P,O,a. P.T.O 7393 7393 in Discuss the structure and bonding obtain the following: (c) formed (c) How will you Diborane. What are the products borazine ammonia (i) B-bromoborazine from when diborane reacts with excess 5 (ii) (NPF,), from (NPCl,), at (i) low temperature Lithium is different from other 2. (a) Chemistry of (ii) high temperature of alkali metals. Give examples in support 5 3515 the statement. 4. Give reason (any five): the gases? more stable than P, (b) What are clathrate compounds of noble (i) P, molecule is clathrates? Why do helium and neon not form molecule. 5 from B to Al but (ii) lonization energy decreases Ga. of increases from Al to Give one method of preparation (c) but a gas at room is the a liquid H,S peroxodisulphuric acid.
    [Show full text]
  • Amide, and Paratoluenesulfonamide on the Amide of Silver,On the Imides
    68 CHEMISTRY: E. C. FRANKLIN METALLIC SALTS OF AMMONO ACIDS By Edward C. Franklin DEPARTMENT OF CHEMISTRY, STANFORD UNIVERSITY Presented to the Academy, January 9. 1915 The Action of Liquid-Ammonia Solutions of Ammono Acids on Metallic Amides, Imides, and Nitrides. The acid amides and imides, and the metallic derivatives of the acid amides and imides are the acds, bases, and salts respectively of an ammonia system of acids, bases, and salts.1 Guided by the relationships implied in the above statement Franklin and Stafford were able to prepare potassium derivatives of a considerable number of acid amides by the action of potassium amide on certain acid amides in solution in liquid ammonia. That is to say, an ammono base, potassium amide, was found to react with ammono acids in liquid ammonia to form ammono salts just as the aquo base, potassium hydrox- ide, acts upon aquo acids in water solution to form aquo salts. Choos- ing, for example, benzamide and benzoic acid as representative acids of the two systems, the analogous reactions taking place respectively in liquid ammonia and water are represented by the equations: CH6CONH2+KNH2 = C6H5CONHK + NHs. CseHCONH2 + 2KNH2 = CIHsCONK2 + 2NH3. CH6tCOOH + KOH = CIH6COOK + H2O. The ammono acid, since it is dibasic, reacts with either one or two molecules of potassium amide to form an acid and a neutral salt. Having thus demonstrated the possibility of preparing ammono salts of potassium by the interaction of potassium amide and acid amides in liquid ammonia solution, it was further found that ammono salts of the heavy metals may be prepared by the action of liquid ammonia solutions of ammono acids on insoluble metallic amides, imides, and nitrides-that is, by reactions which are analogous to the formation of aquo salts in water by the action of potassium hydroxide on insoluble metallic hydroxides and oxides.
    [Show full text]
  • Amide Activation: an Emerging Tool for Chemoselective Synthesis
    Featuring work from the research group of Professor As featured in: Nuno Maulide, University of Vienna, Vienna, Austria Amide activation: an emerging tool for chemoselective synthesis Let them stand out of the crowd – Amide activation enables the chemoselective modification of a large variety of molecules while leaving many other functional groups untouched, making it attractive for the synthesis of sophisticated targets. This issue features a review on this emerging field and its application in total synthesis. See Nuno Maulide et al., Chem. Soc. Rev., 2018, 47, 7899. rsc.li/chem-soc-rev Registered charity number: 207890 Chem Soc Rev View Article Online REVIEW ARTICLE View Journal | View Issue Amide activation: an emerging tool for chemoselective synthesis Cite this: Chem. Soc. Rev., 2018, 47,7899 Daniel Kaiser, Adriano Bauer, Miran Lemmerer and Nuno Maulide * It is textbook knowledge that carboxamides benefit from increased stabilisation of the electrophilic carbonyl carbon when compared to other carbonyl and carboxyl derivatives. This results in a considerably reduced reactivity towards nucleophiles. Accordingly, a perception has been developed of amides as significantly less useful functional handles than their ester and acid chloride counterparts. Received 27th April 2018 However, a significant body of research on the selective activation of amides to achieve powerful DOI: 10.1039/c8cs00335a transformations under mild conditions has emerged over the past decades. This review article aims at placing electrophilic amide activation in both a historical context and in that of natural product rsc.li/chem-soc-rev synthesis, highlighting the synthetic applications and the potential of this approach. Creative Commons Attribution 3.0 Unported Licence.
    [Show full text]
  • Reactions of Benzene & Its Derivatives
    Organic Lecture Series ReactionsReactions ofof BenzeneBenzene && ItsIts DerivativesDerivatives Chapter 22 1 Organic Lecture Series Reactions of Benzene The most characteristic reaction of aromatic compounds is substitution at a ring carbon: Halogenation: FeCl3 H + Cl2 Cl + HCl Chlorobenzene Nitration: H2 SO4 HNO+ HNO3 2 + H2 O Nitrobenzene 2 Organic Lecture Series Reactions of Benzene Sulfonation: H 2 SO4 HSO+ SO3 3 H Benzenesulfonic acid Alkylation: AlX3 H + RX R + HX An alkylbenzene Acylation: O O AlX H + RCX 3 CR + HX An acylbenzene 3 Organic Lecture Series Carbon-Carbon Bond Formations: R RCl AlCl3 Arenes Alkylbenzenes 4 Organic Lecture Series Electrophilic Aromatic Substitution • Electrophilic aromatic substitution: a reaction in which a hydrogen atom of an aromatic ring is replaced by an electrophile H E + + + E + H • In this section: – several common types of electrophiles – how each is generated – the mechanism by which each replaces hydrogen 5 Organic Lecture Series EAS: General Mechanism • A general mechanism slow, rate + determining H Step 1: H + E+ E El e ctro - Resonance-stabilized phile cation intermediate + H fast Step 2: E + H+ E • Key question: What is the electrophile and how is it generated? 6 Organic Lecture Series + + 7 Organic Lecture Series Chlorination Step 1: formation of a chloronium ion Cl Cl + + - - Cl Cl+ Fe Cl Cl Cl Fe Cl Cl Fe Cl4 Cl Cl Chlorine Ferric chloride A molecular complex An ion pair (a Lewis (a Lewis with a positive charge containing a base) acid) on ch lorine ch loronium ion Step 2: attack of
    [Show full text]
  • Ester Resveratrol Analogues, Chromium Trioxide Oxidation of Terpenes, and Synthesis of Mimics of (-)-Englerin A
    Brigham Young University BYU ScholarsArchive Theses and Dissertations 2014-08-01 Synthesis of 4'-Ester Resveratrol Analogues, Chromium Trioxide Oxidation of Terpenes, and Synthesis of Mimics of (-)-Englerin A Mark Jeffrey Acerson Brigham Young University - Provo Follow this and additional works at: https://scholarsarchive.byu.edu/etd Part of the Biochemistry Commons, and the Chemistry Commons BYU ScholarsArchive Citation Acerson, Mark Jeffrey, "Synthesis of 4'-Ester Resveratrol Analogues, Chromium Trioxide Oxidation of Terpenes, and Synthesis of Mimics of (-)-Englerin A" (2014). Theses and Dissertations. 5458. https://scholarsarchive.byu.edu/etd/5458 This Dissertation is brought to you for free and open access by BYU ScholarsArchive. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of BYU ScholarsArchive. For more information, please contact [email protected], [email protected]. Synthesis of 4’-Ester Resveratrol Analogues, Chromium Trioxide Oxidation of Terpenes, and Synthesis of Mimics of (–)-Englerin A Mark Jeffrey Acerson A dissertation submitted to the faculty of Brigham Young University in partial fulfillment of the requirements for the degree of Doctor of Philosophy Merritt B. Andrus, Chair Steven L. Castle Matt A. Peterson Joshua L. Price Richard K. Watt Department of Chemistry and Biochemistry Brigham Young University August 2014 Copyright © 2014 Mark Jeffrey Acerson All Rights Reserved ABSTRACT Synthesis of 4’-Ester Resveratrol Analogues, Chromium Trioxide Oxidation of Terpenes, and Synthesis of Mimics of (–)-Englerin A Mark Jeffrey Acerson Department of Chemistry and Biochemistry, BYU Doctor of Philosophy 4’-ester analogues of resveratrol were synthesized using reaction conditions developed to produce mono-ester products in the presence of two other unprotected phenols.
    [Show full text]
  • Dehydrogenation of Ethanol to Acetaldehyde Over Different Metals Supported on Carbon Catalysts
    catalysts Article Dehydrogenation of Ethanol to Acetaldehyde over Different Metals Supported on Carbon Catalysts Jeerati Ob-eye , Piyasan Praserthdam and Bunjerd Jongsomjit * Center of Excellence on Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand; [email protected] (J.O.-e.); [email protected] (P.P.) * Correspondence: [email protected]; Tel.: +66-2-218-6874 Received: 29 November 2018; Accepted: 27 December 2018; Published: 9 January 2019 Abstract: Recently, the interest in ethanol production from renewable natural sources in Thailand has been receiving much attention as an alternative form of energy. The low-cost accessibility of ethanol has been seen as an interesting topic, leading to the extensive study of the formation of distinct chemicals, such as ethylene, diethyl ether, acetaldehyde, and ethyl acetate, starting from ethanol as a raw material. In this paper, ethanol dehydrogenation to acetaldehyde in a one-step reaction was investigated by using commercial activated carbon with four different metal-doped catalysts. The reaction was conducted in a packed-bed micro-tubular reactor under a temperature range of 250–400 ◦C. The best results were found by using the copper doped on an activated carbon catalyst. Under this specified condition, ethanol conversion of 65.3% with acetaldehyde selectivity of 96.3% at 350 ◦C was achieved. This was probably due to the optimal acidity of copper doped on the activated carbon catalyst, as proven by the temperature-programmed desorption of ammonia (NH3-TPD). In addition, the other three catalyst samples (activated carbon, ceria, and cobalt doped on activated carbon) also favored high selectivity to acetaldehyde (>90%).
    [Show full text]
  • ACETIC ACID and ACETIC ANHYDRIDE (November 1994)
    Abstract Process Economics Program Report 37B ACETIC ACID AND ACETIC ANHYDRIDE (November 1994) This Report presents preliminary process designs and estimated economics for the manufacture of acetic acid and acetic anhydride by carbonylation technology. The three processes evaluated in this report include Monsanto’s low pressure carbonylation of methanol process (BP Chemical acquired licensing rights to this process in 1985), Eastman’s process for carbonylation of methyl acetate to produce acetic anhydride (methanol added to the reaction mixture results in the coproduction of acetic acid in this process), and a process based on BP Chemical patents that coproduces acetic acid and acetic anhydride via carbonylation of methyl acetate in the presence of water. Both the Eastman and BP Chemical processes are back– integrated into the manufacture of the methyl acetate feedstock from methanol and acetic acid. We have included a discussion of other commercialized acetic acid and acetic anhydride processes as well as potential new processes. A list of the world’s acetic acid and acetic anhydride producers along with their estimated plant capacities and a description of the major acetic acid and acetic anhydride markets are also included in this Report. This Report will be useful to producers of acetic acid and acetic anhydride, as well as to producers of methanol and downstream products such as vinyl acetate monomer. PEP’93 MKG CONTENTS 1 INTRODUCTION 1-1 2 SUMMARY 2-1 GENERAL ASPECTS 2-1 ECONOMIC ASPECTS 2-1 TECHNICAL ASPECTS 2-3 Low Pressure Carbonylation
    [Show full text]
  • Experiment #4 the Preparation of Ferrocene & Acetylferrocenes1
    Experiment #4: The Preparation of Ferrocene & Acetylferrocene MASSACHUSETTS INSTITUTE OF TECHNOLOGY Department of Chemistry 5.311 Introductory Chemical Experimentation EXPERIMENT #4 THE PREPARATION OF FERROCENE & ACETYLFERROCENES1 I. Purpose The principal aims of this experiment are to provide background information about and experience in: S the synthesis and electronic structure of ferrocene (1), ( -C5H5)2Fe [bis(pentahaptocyclopentadienyl) iron]2 S the synthesis of an ionic liquid, as environment for the acetylation of ferrocene S the use of inert atmospheres (including glove box techniques) S recrystallization or sublimation S the use of GC/MS and thin-layer chromatography as analytical tools and column chromatography as a purification technique • the concepts of Green Chemistry such as Atom Economy3 and alternative non-polluting solvents Ferrocene is a historically important molecule. The initial recognition of the structure of 4 C10H10Fe in 1951 spawned a vast area of chemistry, viz., transition metal organometallic chemistry. This field is still developing and has produced a huge number of compounds in which saturated, unsaturated, and aromatic organic fragments are bonded directly to metals. All carbon atoms in the two cyclopentadienyl rings are equally bonded to the central ion by electrons in the rings. The sandwich structure proposed by Wilkinson and Fischer5,6 (Nobel prize in 1973) in early 1 Mircea D. Gheorghiu designed the experiment to include the acetylation of ferrocene in ionic liquid. 2 The word hapto means in Greek to fasten. Pentahapto therefore, is to be taken as “fastened in five places.” The greek letter followed by a superscript indicates how many atoms of the ligand are attached to the metal.
    [Show full text]
  • Acetic Anhydride
    ACETIC ANHYDRIDE Method number: 102 Matrix: Air Target concentration: 5 ppm (20 mg/m3) OSHA PEL: 5 ppm (20 mg/m3) TWA ACGIH TLV: 5 ppm (20 mg/m3) ceiling Procedure: Samples are collected open face on glass fiber filters coated with veratrylamine and di-n-octyl phthalate. Samples are extracted with 50/50 (v/v) 2-propanol/toluene and analyzed by GC using a nitrogen- phosphorus detector (NPD). Recommended air volume and sampling rate: 7.5 L at 0.5 L/min ceiling 7.5 L at 0.05 L/min TWA Reliable quantitation limit: 0.094 ppm (0.39 mg/m3) Standard error of estimate at the target concentration: 6.4% Special caution: Ketene and acetyl chloride produce the same derivative as acetic anhydride. Coated filters should be used within a month of preparation. Status of method: Evaluated method. This method has been subjected to the established evaluation procedures of the Organic Methods Evaluation Branch. Date: October 1993 Chemist: Yihlin Chan Organic Methods Evaluation Branch OSHA Salt Lake Technical Center Salt Lake City, UT 84165-0200 1. General Discussion 1.1 Background 1.1.1 History In OSHA Method 82, acetic anhydride is collected on a glass fiber filter impregnated with 1-(2-pyridyl)piperazine, which reacts with the anhydride to form a derivative (Ref. 5.1). Attempts at using 1-(2-pyridyl)piperazine for the derivatization of maleic, phthalic, and trimellitic anhydrides failed, however, because the resulting derivatives of these anhydrides were found to be unstable. These anhydrides were derivatized with veratrylamine instead (Refs. 5.2-5.4).
    [Show full text]
  • Xbridge Amide Columns
    [ PRODUCT SOLUTION ] XBRIDGE AMIDE COLUMNS O O O Si Linker O NH 2 Particle Type: Ethylene Bridged Hybrid [BEH] Ligand Type: Trifunctional Amide Particle Size: 3.5 µm Ligand Density: 7.5 µmol/m2 Carbon Load: 12% Endcap Style: None pH Range: 2-11 Pressure Tolerance: 400 bar HYDROPHILIC INTERacTION CHROMATOGRAPHY XBridge Amide Analysis of Ginsenoside Rb1 Since 2003, Waters has developed innovative stationary phases Orento extract for Hydrophilic Interaction Chromatography [HILIC] to overcome the 0.010 challenge of retaining and separating extremely polar compounds. 0.008 Based on Waters novel ethylene bridged hybrid [BEH] particle 0.006 AU technology, NEW XBridge™ Amide columns utilize a chemically stable, 0.004 0.002 Ginsenoside Rb1 trifunctionally-bonded amide phase, enabling a new dimension in 0.000 stability and versatility for HILIC separations. XBridge Amide columns offer the same selectivity as ACQUITY UPLC® BEH Amide columns, 20 µg/mL Ginsenoside Rb1 standard allowing scientists to transfer their separations between HPLC and 0.010 ® UPLC technology platforms. 0.008 0.006 Designed to retain polar analytes and metabolites that are too polar AU 0.004 to retain by reversed-phase [RP] chromatography, XBridge Amide 0.002 columns facilitate the use of a wide range of mobile phase pH [2 – 11] 0.000 Ginsenoside Rb1 to facilitate the exceptional retention of polar analytes spanning a 0.00. 5 1.01. 5 2.02. 5 3.03. 5 4.04. 5 5.05. 5 6.06. 5 min wide range in polarity, structural moiety and pKa. Column: XBridge Amide, 3.5 µm, 4.6 x 150 mm Part Number: 186004869 Mobile Phase : 80/20 ACN/H2O In addition to enhanced retention of polar compounds, XBridge Flow Rate: 1.4 mL/min Inj.
    [Show full text]